WO2015193202A1 - Herbicidal compounds - Google Patents

Abstract

The invention relates to dihydro-hydantoincompounds of the formula (I) wherein X, R^b, R^c, R² and R³ are as defined in the specification. Furthermore, the present invention relates to processes and intermediates for making compounds of formula (I), to herbicidal compositions comprising these compounds and to methods of using these compounds to control plant growth.

Description

HERBICIDAL COMPOUNDS

The present invention relates to certain substituted dihydro-hydantoin derivatives, to processes for their preparation, herbicidal compositions comprising them, and their use in controlling plants or inhibiting plant growth.

Herbicidal dihydro-hydantoins of the formula

wherein A is an isoxazole ring are taught in e.g. US Patent No. 4,302,239 and Canadian Patent No. 1205077.

Summary of the Invention

Surprisingly, it has now been found that, for a certain group of dihydro-hydantoin compounds substituted with an isoxazole ring, herbicidal activity resides almost completely in compounds with R stereochemistry at the carbon containing the R² substituent (as shown in formula (I)).

Accordingly, in a first aspect, the invention provides compounds of the formula (I)

(I)

wherein

X is selected from S and O;

R^b is selected from Ci-C₆ alkyl, Ci-C₆ cyanoalkyl, C₃-C₆ cycloalkyl, C₃-C₆ cyanocycloalkyl, Ci-C₆ haloalkyl and Ci-C₆ alkylthio;

R^c is selected from hydrogen, halogen, cyano, Ci-C₆ alkyl and Ci-C₆ haloalkyl; - - or R^b and R^c together with the carbon atoms to which they are attached form a 3-7 membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms

independently selected from S, O and N and optionally substituted with from 1 to 3 groups independently selected from halogen, Ci-C₆ alkyl and Ci-C₆ haloalkyi; R² is selected from Ci-C₄ alkoxy and Ci-C₄ alkoxy-Ci-C₄ alkyl;

R³ is selected from halogen, hydroxyl, -NR⁵R⁶ andany one of the following groups

R⁵ and R⁶ are independently selected from hydrogen, Ci-C₂o alkyl, Ci-C₂o haloalkyi, C₂-C₂o alkenyl, C₂-C₂₀ alkynyl, or R⁵ and R⁶ together with the carbon atoms to which they are attached form a 3-6 membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms independently selected from S, O and N and optionally substituted with from 1 to 3 groups independently selected from halogen and Ci-C₆ alkyl;

R⁷ and R⁸ are independently selected from hydrogen, Ci-C₆ alkyl, Ci-C₆ haloalkyi, C₂-C₆ alkenyl, C₂-C₆ alkynyl, a C₅-Ci₀ heteroaryl group which can be mono- or bicyclic comprising from 1 to 4 heteroatoms independently selected from N, O and S and optionally substituted with 1 to 3 groups independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyi and C1-C3 alkoxy, a C₆- C-io aryl group optionally substituted with 1 to 3 groups independently selected from halogen, nitro, cyano, C1-C3 alkyl, Ci-C₃ alkoxy, Ci-C₃ haloalkyi and Ci-C₃ haloalkoxy, or R⁷ and R⁸ together with the atoms to which they are attached form a 3-6 membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms independently selected from S, O and N and optionally substituted with from 1 to 3 groups independently selected from halogen or d-C₆ alkyl;

R⁹ is selected from Ci-C₆ alkyl or benzyl optionally substituted with 1 to 3 groups independently selected from halogen, nitro, cyano, Ci-C₃ alkyl, Ci-C₃ alkoxy, Ci-C₃ haloalkyi and Ci-C₃ haloalkoxy; or an N-oxide or salt form thereof and wherein the dihydro-hydantoin ring carbon to which R² is attached has the R-stereochemistry as depicted.

Detailed Description - -

In particularly preferred embodiments of the invention, the preferred groups for X, R^b, R^c, R² and R³, in any combination thereof, are as set out below.

Preferably, X is O.

Preferably, R^b is selected from Ci-C₆ alkyl, Ci-C₆ cyanoalkyl, C₃-C₆ cycloalkyl, C₃-C₆ cyanocycloalkyl, Ci-C₆ haloalkyl and Ci-C₆ alkylthio. More preferably, R^b is selected from C₁-C4 alkyl, C₁-C4 cyanoalkyl, C₃-C₆ cycloalkyl, C₃-C₆ cyanocycloalkyl, C₁-C4 haloalkyl and C₁-C4 alkylthio. Even more preferably, R^b is selected from C₁-C4 alkyl or C₁-C4 haloalkyl. Most preferably, R^b is tert-butyl or 1-fluoro-1 -methyl-ethyl.

Preferably, R^c is selected from hydrogen, chloro, fluoro, bromo, cyano, C₁-C4 alkyl and d- C₄ haloalkyl. More preferably, R^c is hydrogen, chloro, fluoro, cyano or methyl. Most preferably, R^c is hydrogen.

In a preferred embodiment, the isoxazole ring is 5-tert-butylisoxazol-3-yl.

Preferably R² is selected from Ci-C₃ alkoxy and Ci-C₃ alkoxy-Ci-C₃ alkyl. More preferably R² is selected from methoxy, ethoxy, propyloxy, methoxymethyl, ethoxymethyl and methoxyethyl. More preferably, R² is selected from methoxy, ethoxy and propyloxy.

Preferably, R³ is selected from hydroxyl, -NR⁵R⁶, halogen, Ci-C₆ alkylcarbonyloxy, Ci-C₆ alkoxycarbonyloxy or aryloxycarbonyloxy wherein the aryl group may be substituted with 1 to 3 groups independently selected from halogen, nitro, cyano, Ci-C₃ alkyl, Ci-C₃ alkoxy, Ci-C₃ haloalkyl and Ci-C₃ haloalkoxy. More preferably, R³ is selected from hydroxyl, -NR⁵R⁶ or halogen. Most preferably, R³ is hydroxyl.

In a preferred embodiment, the invention provides the compounds A1 to A5 as shown in

Table 1.

In addition, in another aspect, the present invention also provides the following novel compounds of formula (la):

(la) wherein - -

X is selected from S and O;

R^b is selected from Ci-C₆ alkyl, Ci-C₆ cyanoalkyl, C₃-C₆ cycloalkyl, C₃-C₆ cyanocycloalkyl, Ci-C₆ haloalkyi and Ci-C₆ alkylthio;

R^c is selected from hydrogen, halogen, cyano, Ci-C₆ alkyl and Ci-C₆ haloalkyi; or R^b and R^c together with the carbon atoms to which they are attached form a 3-7 membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms

independently selected from S, O and N and optionally substituted with from 1 to 3 groups independently selected from halogen, Ci-C₆ alkyl and Ci-C₆ haloalkyi;

R² is selected from ethoxy, propyloxy and Ci-C₄ alkoxy-Ci-C₄ alkyl; R³ is selected from halogen, hydroxyl, -NR⁵R⁶ and any one of the following groups

R⁵ and R⁶ are independently selected from hydrogen, Ci-C₂o alkyl, Ci-C₂o haloalkyi, C₂-C₂o alkenyl, C₂-C₂₀ alkynyl, or R⁵ and R⁶ together with the carbon atoms to which they are attached form a 3-6 membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms independently selected from S, O and N and optionally substituted with from 1 to 3 groups independently selected from halogen and Ci-C₆ alkyl;

R⁷ and R⁸ are independently selected from hydrogen, Ci-C₆ alkyl, Ci-C₆ haloalkyi, C₂-C₆ alkenyl, C₂-C₆ alkynyl, a C₅-Ci₀ heteroaryl group which can be mono- or bicyclic comprising from 1 to 4 heteroatoms independently selected from N, O and S and optionally substituted with 1 to 3 groups independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyi and Ci-C₃ alkoxy, a C₆- C-io aryl group optionally substituted with 1 to 3 groups independently selected from halogen, nitro, cyano, Ci-C₃ alkyl, Ci-C₃ alkoxy, Ci-C₃ haloalkyi and Ci-C₃ haloalkoxy, or R⁷ and R⁸ together with the atoms to which they are attached form a 3-6 membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms independently selected from S, O and N and optionally substituted with from 1 to 3 groups independently selected from halogen or d-C₆ alkyl; - -

R is selected from Ci-C₆ alkyl or benzyl optionally substituted with 1 to 3 groups independently selected from halogen, nitro, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl and C1-C3 haloalkoxy; or an N-oxide or salt form thereof. Preferred substituents for X, R^b, R^c and R³ are as given above,

Preferably, R² is selected from methoxy, ethoxy, propyloxy, methoxymethyl, ethoxymethyl and methoxyethyl. More preferably, R² is selected from methoxy, ethoxy and propyloxy.

In preferred embodiments of this aspect, the invention provides a compound selected from

The compounds the invention may exist as different geometric isomers, or in different tautomeric forms. This invention covers all such isomers and tautomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds.

The compounds of the invention contain one or more asymmetric centers and may thus give rise to optical isomers and diastereomers. While some asymmetric centers are shown without respect to stereochemistry, the present invention includes all such optical isomers and diastereomers; as well as the racemic and resolved, enantiomerically pure R and S

stereoisomers; as well as other mixtures of the R and S stereoisomers and agrochemically acceptable salts thereof. It is recognized that certain optical isomers or diastereomers may have favorable properties over the others. Thus when disclosing and claiming the invention, when one racemic mixture is disclosed, it is clearly contemplated that both optical isomers, including diastereomers, substantially free of the other are disclosed and claimed as well.

Alkyl, as used herein refers to an aliphatic hydrocarbon chain and includes straight and branched chains e. g. of 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, and isohexyl.

Alkenyl, as used herein, refers to an aliphatic hydrocarbon chain having at least one double bond, and preferably one double bond, and includes straight and branched chains e. g. of 2 to 8 carbon atoms such as ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), isopropenyl, but-1- enyl, but-2-enyl, but-3-enyl, 2-methypropenyl. - -

Alkynyl, as used herein, refers to an aliphatic hydrocarbon chain having at least one triple bond, and preferably one triple bond, and includes straight and branched chains e. g. of 2 to 8 carbon atoms such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl) but-1-ynyl, but-2-ynyl and but- 3-ynyl.

Cycloalkyl, as used herein, refers to a cyclic, saturated hydrocarbon group having from 3 to 6 ring carbon atoms. Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Alkoxy as used herein refers to the group -OR, wherein R is alkyl as defined above.

Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentoxy, isopentoxy, neo-pentoxy, n-hexyloxy, and isohexyloxy.

Alkoxyalkyl as used herein refers to the group -ROR, wherein each R is, independently, an alkyl group as defined above.

Cyanoalkyl as used herein refers to an alkyl group substituted with one or more cyano groups.

Cyanocycloalkyl as used herein refers to an cycloalkyl group substituted with one or more cyano groups.

Halogen, halide and halo refer to iodine, bromine, chlorine and fluorine.

Haloalkyi as used herein refers to an alkyl group as defined above wherein at least one hydrogen atom has been replaced with a halogen atom as defined above. Examples of haloalkyi groups include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and trifluoromethyl. Preferred haloalkyi groups are fluoroalkyi groups {i.e. haloalkyi groups, containing fluorine as the only halogen). More highly preferred haloalkyi groups are perfluoroalkyl groups, i.e. alkyl groups wherein all the hydrogen atoms are replaced with fluorine atoms.

Haloalkoxy as used herein refers to the group -OR, wherein R is haloalkyi as defined above.

Alkylthio as used herein refers to the group -SR, wherein R is an alkyl group as defined above. Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tert- butylthio, and the like.

Alkycarbonyloxy, as used herein, refers to the group -OC(0)R, wherein R is an alkyl group as defined above.

Alkoxycarbonyloxy as used herein, refers to the group -OC(0)OR, wherein R is an alkyl group as defined above. Examples of alkoxycarbonyloxy groups are methoxycarbonyloxy, ethoxycarbonyloxy, propoxycarbonyloxy, but-1-oxycarbonyloxy, but-2-oxycarbonyloxy and but-3- oxycarbonyloxy. - -

Hydroxy or hydroxyl, as used herein, refers to the group -OH.

Nitro, as used herein, refers to the group -N0₂. Cyano as used herein, refers to the group -CN.

Aryl, as used herein, refers to an unsaturated aromatic carbocyclic group of from 6 to 10 carbon atoms having a single ring (e. g., phenyl) or multiple condensed (fused) rings, at least one of which is aromatic (e.g., indanyl, naphthyl). Preferred aryl groups include phenyl, naphthyl and the like. Most preferably, an aryl group is a phenyl group.

Aryloxycarbonyloxy as used herein, refers to the group -OC(0)0-aryl wherein aryl is a as defined above. Benzyl, as used herein, refers to the group -CH₂C₆H₅.

Heteroaryl, as used herein, refers to a ring system containing 5 to 10 ring atoms, 1 to 4 ring heteroatoms and consisting either of a single aromatic ring or of two or more fused rings, at least one of which is aromatic. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be independently chosen from nitrogen, oxygen and sulfur. Examples of such groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl. Examples of bicyclic groups are benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl and pyrazolo[1 ,5-a]pyrimidinyl. 'Saturated ring', as used herein, refers to a ring system in which the atoms in the ring are linked by single bonds.

'Partially unsaturated ring', as used herein, refers to a ring system in which at least two atoms in the ring are linked by a double bond. Partially unsaturated ring systems do not include aromatic rings. 'Optionally substituted' as used herein means the group referred to can be substituted at one or more positions by any one or any combination of the radicals listed thereafter. For most groups, one or more hydrogen atoms are replaced by the radicals listed thereafter. For halogenated groups, for example, haloalkyi groups, one or more halogen atoms are replaced by the radicals listed thereafter. Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula N⁺(R ⁹R²⁰R² R²²) wherein R ⁹, R²⁰, R² and R²² are independently selected from hydrogen, Ci-C₆ alkyl and Ci-C₆ hydroxyalkyl. Salts of the compounds of formula (I) can be prepared by treatment of compounds of formula (I) with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, - - diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine. Amine salts are often preferred forms of the compounds of formula (I) because they are water-soluble and lend themselves to the preparation of desirable aqueous based herbicidal compositions. Acceptable salts can be formed from organic and inorganic acids, for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids when a compound of this invention contains a basic moiety. In another aspect the present invention provides intermediates useful in the preparation of compounds of the invention.

In one embodiment, there are provided intermediates of the formula (II), wherein X, R², R^b and R^c are as defined above. These intermediates can also display herbicidal activity.

(II)

In another embodiment, there are provided intermediates of the formula (III) wherein X, R' and R^c are as defined above.

(Ml)

Compounds of the invention may be prepared by techniques known to the person skilled in the art of organic chemistry. General methods for the production of compounds of formula (I) and - -

(la) are described below. Unless otherwise stated in the text, the substituents X, R², R³, R^b and R^c are as defined hereinbefore. The starting materials used for the preparation of the compounds of the invention may be purchased from usual commercial suppliers or may be prepared by known methods. The starting materials as well as the intermediates may be purified before use in the next step by state of the art methodologies such as chromatography, crystallization, distillation and filtration.

For example, compounds of formula (IX) wherein R is a methyl group and R² is an alkoxy- alkyl group may be prepared by reaction of amino-isoxazole (IV) with phenylchloroformate to give carbamate product (V). The subsequent reaction with an appropriately substutited amino-ester (VI) gives compounds of type (VII) and subsequent cyclisation gives compounds of type (VIII) and reduction with e.g. with sodium borohydride gives compounds of type (IX). The methyl amino-ester (VI) may also be replaced by other amino esters or amino-acids. Phenyl chloroformate may be replaced by other activating groups such as phosgene or para-nitrophenyl chlorofomate. The cyclisation to (VIII) may occur in situ or require heating for carboxylic acids or esters or treatment with a reagent such as thionyl chloride for carboxylic acids. Esters of type

(VII) may also be reduced to their corresponding primary alcohols and then such alcohols can be re-oxidised to compounds of type (IX) with oxidants such as Dess-Martin periodinane.

Alternatively, carbamate (V) can be reacted with amines of type (XXXVII) to afford compounds of type (XXXVIII) which upon subsequent cyclisation, with the appropriate acid, such as acetic acid, hydrochloric acid, p-toluenesulfonic acid, afford compounds of type (IX). - -

Intermediates of formula (X) wherein R² is an hydroxy group may be prepared by the reaction of compounds of type (V) with an appropriate amine (XI) to give urea (XII), which can react with aqueous glyoxal solution to give product (X). Compounds of formula (IX) where R₂ is an alkoxy group may be prepared by reacting compounds of formula (X) with alcohols of type R₄- OH under acidic conditions.

Alternatively oxidative cleavage (using ozonolysis or Os0₄/Nal0₄ or similar conditions) of an appropriate vinyl compound such as (XIII) or derivatives thereof and cyclisation could give the desired product.

Amino-isoxazoles are commercially available or may be made by standard procedures such as those outlined below.

The relevant amino isoxazoles (XXIV) can be prepared by methods well known in the art, described e.g. in Gilchrist, T. L, Heterocyclic Chemistry (1992), 2^nd Ed, Longman Scientifc & Technical and John Wiley & Sons. A substituted oxonitrile (XXIII) may be treated with hydroxyl amine under appropriate conditions of pH and temperature which is described, for example, in Takase et al Heterocycles 1991 , 32(6), 1 153-1 158, to afford the desired isoxazole amine product (XXIV). This method is particularly applicable for cases in which R^b is sterically demanding. - -

solvent, heat

(XXIII) (XXIV)

Depending on R^b, in order to influence the yield and regiochemical outcome of the condensation reaction, the substituted oxonitrile (XXIII) may be productively replaced in the forgoing scheme by oxo-protected derivatives, such as a ketal derivative (XXV, R^d= lower alkyl or taken together, an alkylene derivative to form a ketal ring). These derivatives are prepared from the corresponding (XXIII) under standard conditions for example as described in Chan et al. Synthesis 1983 203-205.

(XXV)

Compounds (XXVI) where R^b is as defined above may be halogenated (i) under standard conditions to access intermediates (XXVII) where X is chlorine, bromine or iodine. (XXVI) can also be alkylated (ii) to form (XXIV), where R^c is methyl or ethyl. These transformations are known in the literature and described, for example in WO2007100295 and Tetrahedron Letters, 2008, 49, 1 , p. 189.

(XXIV) (XXVII)

(XXVI)

3-amino-4-nitrile substituted isoxazoles (XXVIII) may be prepared as shown below, as reported in the literature DE 2249163 A1 - -

(XXVIII)

(XXXI)

Nitrile vinyl chlorides (XXXI) can be prepared from the corresponding β-ketonitrile (XXXII) and a suitable chlorination reagent such as PCI₅ or POCI₃, in a suitable solvent, such as dichloromethane as shown in Scheme 10. Chlorination,

solvent, heating

(XXXII)

(XXXI)

Below is shown the preparation of the requisite 3-oxonitriles (XXIII) by reaction of an containing carboxylic ester (XXXIII) with an alkali metal salt of acetonitrile (XXXIV) (see for example US 4,728,743).

(XXXIII)

(XXXIV) (XXIII)

Alternatively, compounds of formula XXXII may be prepared by reaction of R^b containing acid chloride (XXXV) and an alkali metal salt of malononitrile (XXXVI) (for example DE 2249163

(XXXV) (xxxvi) (XXXII)

Suitable conditions for effecting these transformations are set out in texts such as J. March, Advanced Organic Chemistry, 4th ed. Wiley, New York, 1992.

The compounds of formula (I) and (la) according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. Therefore, the invention also relates to a herbicidal composition - - which comprises a herbicidally effective amount of a compound of formula (I) or (la) in addition to formulation adjuvants.

In practice, the R-enantiomer (i.e. the compound of formula (I)) may not be in its 100% pure form. As such, the proportion of R-enantiomer in the compositions of the invention is at least 55%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% w/w. Where the proportion of R- enantiomer is below 100%, the remainder of the active ingredient is, of course, made up of the equivalent S-enantiomer.

The formulations of the invention can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. Such formulations can either be used directly or they are diluted prior to use. The dilutions can be made, for example, with water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).

Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid - - anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2- dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N- dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 , 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesu Ifonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydro- furfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2- pyrrolidone and the like. Water is generally the carrier of choice for diluting the concentrates.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001. (c) & (d). A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as

diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecyl- benzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium

dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkylphosphate esters; and also further substances described e.g. in "McCutcheon's

Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981. - -

Further adjuvants that can usually be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralizing or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilizers.

The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhone-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C₈-C₂₂ fatty acids, especially the methyl derivatives of Ci₂-Ci₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as methyl laurate (CAS-1 1 1- 82-0), methyl palmitate (CAS-1 12-39-0) and methyl oleate (CAS-1 12-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000. The application and action of the oil additives can be further improved by combination with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of the surface-active substances in relation to the total additive is generally from 1 to 30 % by weight. Examples of oil additives consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).

If desired, it is also possible for the mentioned surface-active substances to be used in the formulations on their own, that is to say, without oil additives. - -

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture may contribute to an additional enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80 % by weight of the total weight. Oil additives that are present in admixture with solvents are described, for example, in US-A-4,834,908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).

In addition to the oil additives listed above, for the purpose of enhancing the action of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic lattices, e.g.

polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray mixture as action-enhancing agent.

The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula (I) or (la) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The rates of application of compounds of formula (I) and (la) may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the grass or weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula (I) and (la) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha. In particular, the compounds of formula (I) and (la) according to the invention may be applied at a rate from 62.5 to 500 g/ha and, more particularly at a rate from 62.5 to 250 g/ha.

Preferred formulations have especially the following compositions (% = percent by weight): Emulsifiable concentrates:

active ingredient: 1 to 95 %, preferably 60 to 90 %

surface-active agent: 1 to 30 %, preferably 5 to 20 %

liquid carrier: 1 to 80 %, preferably 1 to 35 %

Dusts:

active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %

solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates: - - active ingredient: 5 to 75 %, preferably 10 to 50 %

water: 94 to 24 %, preferably 88 to 30 %

surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powders:

active ingredient: 0.5 to 90 %, preferably 1 to 80 %

surface-active agent: 0.5 to 20 %, preferably 1 to 15 %

solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules:

active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %

solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The following Examples further illustrate, but do not limit, the invention. Formulation Examples for herbicides of formula (I) (% = % by weight)

F1. Emulsifiable concentrates a) b) c) d) active ingredient 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % 4 % 4 %

(36 mol of ethylene oxide)

octylphenol polyglycol ether 4 % 2 % (7-8 mol of ethylene oxide)

Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.

F2. Solutions

active ingredient

1-methoxy-3-(3-methoxy- propoxy)-propane 20 % 20 %

polyethylene glycol MW 400 20 % 10 %

NMP 30 % 10 % arom. hydrocarbon mixture 75 % 60 %

The solutions are suitable for use in the form of microdrops.

F3. Wettable powders

active ingredient

- - sodium lignosulfonate 3 %

sodium lauryl sulfate 3 % 4 % sodium diisobutylnaphthalene- sulfonate 6 % 5 % 6 % octylphenol polyglycol ether 1 % 2 %

(7-8 mol of ethylene oxide)

highly dispersed silicic acid 3 % 5 % 10 % kaolin

62 % 35 %

The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c)

active ingredient 0.1 % 5 % 15 %

highly dispersed silicic acid 0.9 % 2 % 2 %

inorganic carrier 99.0 % 93 % 83 %

(diameter 0.1 - 1 mm)

e.g. CaC0₃ or Si0₂

The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.

F5. Coated granules a) b) c)

active ingredient 0.1 % 5 % 15 % polyethylene glycol MW 200 1.0 % 2 % 3 %

highly dispersed silicic acid 0.9 % 1 % 2 %

inorganic carrier 98.0 % 92 % 80 %

(diameter 0.1 - 1 mm)

e.g. CaC0₃ or Si0₂

The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

F6. Extruder granules a) b) c) d) active ingredient 0.1 % 3 % 5 % 15 % sodium lignosulfonate 1.5 % 2 % 3 % 4 % carboxymethylcellulose 1.4 % 2 % 2 % 2 % kaolin 97.0 % 93 % 90 % 79 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

F7. Dusts a) b) c) - - active ingredient 0.1 % 1 % 5 %

talcum 39.9 % 49 % 35 %

kaolin 60.0 % 50 % 60 %

Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient 3 % 10 % 25 % 50 % ethylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether 1 % 2 %

(15 mol of ethylene oxide)

sodium lignosulfonate 3 % 3 % 4 % 5 % carboxymethylcellulose 1 % 1 % 1 % 1 % 37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution

silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87 % 79 % 62 % 38 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

The invention also provides a method of controlling plants which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I) or (la).

The invention also provides a method of inhibiting plant growth which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I) of (la).

The invention also provides a method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a compound or a composition of the invention.

The invention also provides a method of selectively controlling grasses and/or weeds in crops of useful plants which comprises applying to the useful plants or locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (I) or (la).

The term "herbicide" as used herein means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on the growth of plants. Controlling or modifying effects include all deviation from natural development, for example: killing, retardation, leaf burn, albinism, dwarfing and the like. The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, - - roots, tubers, stems, stalks, foliage, and fruits. The term "locus" is intended to include soil, seeds, and seedlings, as well as established vegetation and includes not only areas where weeds may already be growing, but also areas where weeds have yet to emerge, and also to areas under cultivation with respect to crops of useful plants. "Areas under cultivation" include land on which the crop plants are already growing and land intended for cultivation with such crop plants. The term "weeds" as used herein means any undesired plant, and thus includes not only

agronomically important weeds as described below, but also volunteer crop plants.

The compounds of the invention can be applied before or after planting of the crops, before weeds emerge (pre-emergence application) or after weeds emerge (post-emergence application), and are particularly effective when applied post-emergence to the weeds.

Crops of useful plants in which the composition according to the invention can be used include, but are not limited to, perennial crops, such as citrus fruit, grapevines, nuts, oil palms, olives, pome fruit, stone fruit and rubber, and annual arable crops, such as cereals, for example barley and wheat, cotton, oilseed rape, maize, rice, soy beans, sugar beet, sugar cane, sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, maize and soy beans.

The grasses and weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eriochloa, Lolium, Monochoria, Panicum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus,

Chenopodium, Chrysanthemum, Euphorbia, Galium, Ipomoea, Kochia, Nasturtium, Polygonum, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

In all aspects of the invention, in a particular embodiment, the weeds, e.g. to be controlled and/or growth-inhibited may be monocotyledonous or dicotyledonous weeds, which are tolerant or resistant to one or more other herbicides for example, HPPD inhibitor herbicides such as mesotrione, PSII inhibitor herbicides such as atrazine or EPSPS inhibitors such as glyphosate. Such weeds include, but are not limited to resistant Amaranthus biotypes.

Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. auxins or ALS-, EPSPS-, PPO- and HPPD- inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate- resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®, respectively.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European - - corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesize such toxins, are described in EP-A-451 878, EP-A- 374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavor). Any method of application to weeds/crop of useful plant, or locus thereof, which is routinely used in agriculture may be used, for example application by spray or broadcast method typically after suitable dilution of a compound of formula (I) or (la) (whether said compound is formulated and/or in combination with one or more further active ingredients and/or safeners, as described herein). The compounds according to the invention can also be used in combination with other active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators. Such mixtures, and the use of such mixtures to control weeds and/or undesired plant growth, form yet further aspects of the invention. For the avoidance of doubt, mixtures of invention also include mixtures of two or more different compounds of formula (I) or (la). In particular, the present invention also relates to a composition of the invention which comprises at least one further herbicide in addition to the compound of formula (I) or (la).

When a compound of formula (I) is combined with at least one additional herbicide, the following mixtures of the compound of formula (I) are preferred. Compound of formula (I) + acetochlor, compound of formula (I) + acifluorfen, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + aclonifen, compound of formula (I) + acrolein, compound of formula (I) + alachlor, compound of formula (I) + alloxydim, compound of formula (I) + allyl alcohol, compound of formula (I) + ametryn, compound of formula (I) + amicarbazone, compound of formula (I) + amidosulfuron, compound of formula (I) + aminocyclopyrachlor, compound of formula (I) + aminopyralid, compound of formula (I) + amitrole, compound of formula (I) + ammonium sulfamate, compound of formula (I) + anilofos, compound of formula (I) + asulam, compound of formula (I) + atrazine, compound of formula (I) + aviglycine, compound of formula (I) + azafenidin, compound of formula (I) + azimsulfuron, compound of formula (I) + BCPC, - - compound of formula (I) + beflubutamid, compound of formula (I) + benazolin, compound of formula (I) + bencarbazone, compound of formula (I) + benfluralin, compound of formula (I) + benfuresate, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron- methyl, compound of formula (I) + bensulide, compound of formula (I) + bentazone, compound of formula (I) + benzfendizone, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bicyclopyrone, compound of formula (I) + bifenox, compound of formula (I) + bilanafos, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + borax, compound of formula (I) + bromacil, compound of formula (I) + bromobutide, compound of formula (I) + bromophenoxim, compound of formula (I) + bromoxynil, compound of formula (I) + butachlor, compound of formula (I) + butafenacil, compound of formula (I) + butamifos, compound of formula (I) + butralin, compound of formula (I) + butroxydim, compound of formula (I) + butylate, compound of formula (I) + cacodylic acid, compound of formula (I) + calcium chlorate, compound of formula (I) + cafenstrole, compound of formula (I) + carbetamide, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + CDEA, compound of formula (I) + CEPC, compound of formula (I) + chlorflurenol, compound of formula (I) + chlorflurenol-methyl, compound of formula (I) + chloridazon, compound of formula (I) + chlorimuron, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + chloroacetic acid, compound of formula (I) + chlorotoluron, compound of formula (I) + chlorpropham, compound of formula (I) + chlorsulfuron, compound of formula (I) + chlorthal, compound of formula (I) + chlorthal-dimethyl, compound of formula (I) + cinidon-ethyl, compound of formula (I) + cinmethylin, compound of formula (I) + cinosulfuron, compound of formula (I) + cisanilide, compound of formula (I) + clethodim, compound of formula (I) + clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + clopyralid, compound of formula (I) + cloransulam, compound of formula (I) + cloransulam-methyl, compound of formula (I) + CMA, compound of formula (I) + 4-CPB, compound of formula (I) + CPMF, compound of formula (I) + 4-CPP, compound of formula (I) + CPPC, compound of formula (I) + cresol, compound of formula (I) + cumyluron, compound of formula (I) + cyanamide, compound of formula (I) + cyanazine, compound of formula (I) + cycloate, compound of formula (I) + cyclosulfamuron, compound of formula (I) + cycloxydim, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D, compound of formula (I) + 3,4-DA, compound of formula (I) + daimuron, compound of formula (I) + dalapon, compound of formula (I) + dazomet, compound of formula (I) + 2,4-DB, compound of formula (I) + 3,4-DB, compound of formula (I) + 2,4-DEB, compound of formula (I) + desmedipham, formula (I) + desmetryn, compound of formula (I) + dicamba, compound of formula (I) + dichlobenil, compound of formula (I) + ortho-dichlorobenzene, compound of formula (I) + para-dichlorobenzene, compound of formula (I) + dichlorprop, compound of formula (I) + dichlorprop-P, compound of formula (I) + diclofop, compound of formula (I) + diclofop-m ethyl, compound of formula (I) + diclosulam, compound of formula (I) + difenzoquat, compound of formula (I) + difenzoquat metilsulfate, compound of formula (I) + diflufenican, compound of formula (I) + diflufenzopyr, compound of - - formula (I) + dimefuron, compound of formula (I) + dimepiperate, compound of formula (I) + dimethachlor, compound of formula (I) + dimethametryn, compound of formula (I) +

dimethenamid, compound of formula (I) + dimethenamid-P, compound of formula (I) + dimethipin, compound of formula (I) + dimethylarsinic acid, compound of formula (I) + dinitramine, compound of formula (I) + dinoterb, compound of formula (I) + diphenamid, formula (I) + dipropetryn, compound of formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of formula (I) + dithiopyr, compound of formula (I) + diuron, compound of formula (I) + DNOC, compound of formula (I) + 3,4-DP, compound of formula (I) + DSMA, compound of formula (I) + EBEP, compound of formula (I) + endothal, compound of formula (I) + EPTC, compound of formula (I) + esprocarb, compound of formula (I) + ethalfluralin, compound of formula (I) + ethametsulfuron, compound of formula (I) + ethametsulfuron-methyl, compound of formula (I) + ethephon, compound of formula (I) + ethofumesate, compound of formula (I) + ethoxyfen, compound of formula (I) + ethoxysulfuron, compound of formula (I) + etobenzanid, compound of formual (I) + fenoxaprop, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + fentrazamide, compound of formula (I) + ferrous sulfate, compound of formula (I) + flamprop-M, compound of formula (I) + flazasulfuron, compound of formula (I) + florasulam, compound of formula (I) + fluazifop, compound of formula (I) + fluazifop-butyl, compound of formula (I) + fluazifop-P, compound of formula (I) + fluazifop-P-butyl, compound of formula (I) + fluazolate, compound of formula (I) + flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of formula (I) + flucetosulfuron, compound of formula (I) + fluchloralin, compound of formula (I) + flufenacet, compound of formula (I) + flufenpyr, compound of formula (I) + flufenpyr- ethyl, compound of formula (I) + flumetralin, compound of formula (I) + flumetsulam, compound of formula (I) + flumiclorac, compound of formula (I) + flumiclorac-pentyl, compound of formula (I) + flumioxazin, compound of formula (I) + flumipropin, compound of formula (I) + fluometuron, compound of formula (I) + fluoroglycofen, compound of formula (I) + f I uoroglycof en-ethyl, compound of formula (I) + fluoxaprop, compound of formula (I) + flupoxam, compound of formula (I) + flupropacil, compound of formula (I) + flupropanate, compound of formula (I) +

flupyrsulfuron, compound of formula (I) + flupyrsulfuron-methyl-sodium, compound of formula (I) + flurenol, compound of formula (I) + fluridone, compound of formula (I) + flurochloridone, compound of formula (I) + fluroxypyr, compound of formula (I) + flurtamone, compound of formula (I) + fluthiacet, compound of formula (I) + fluthiacet-m ethyl, compound of formula (I) + fomesafen, compound of formula (I) + foramsulfuron, compound of formula (I) + fosamine, compound of formula (I) + glufosinate, compound of formula (I) + glufosinate-ammonium, compound of formula (I) + glyphosate, compound of formula (I) + halauxifen, compound of formula (I) + halauxifen- methyl, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl, compound of formula (I) + haloxyfop, compound of formula (I) + haloxyfop-P, compound of formula (I) + HC-252, compound of formula (I) + hexazinone, compound of formula (I) + imazamethabenz, compound of formula (I) + imazamethabenz-methyl, compound of formula (I) + imazamox, compound of formula (I) + imazapic, compound of formula (I) + imazapyr, compound of formula (I) + imazaquin, compound of formula (I) + imazethapyr, compound of formula (I) + - - imazosulfuron, compound of formula (I) + indanofan, compound of formula (I) + indaziflam, compound of formula (I) + iodomethane, compound of formula (I) + iodosulfuron, compound of formula (I) + iodosulfuron-methyl-sodium, compound of formula (I) + ioxynil, compound of formula (I) + ipfencarbazone, compound of formula (I) + isoproturon, compound of formula (I) + isouron, compound of formula (I) + isoxaben, compound of formula (I) + isoxachlortole, compound of formula (I) + isoxaflutole, compound of formula (I) + isoxapyrifop, compound of formula (I) + karbutilate, compound of formula (I) + lactofen, compound of formula (I) + lenacil, compound of formula (I) + linuron, compound of formula (I) + MAA, compound of formula (I) + MAMA, compound of formula (I) + MCPA, compound of formula (I) + MCPA-thioethyl, compound of formula (I) + MCPB, compound of formula (I) + mecoprop, compound of formula (I) + mecoprop- P, compound of formula (I) + mefenacet, compound of formula (I) + mefluidide, compound of formula (I) + mesosulfuron, compound of formula (I) + mesosulfuron-methyl, compound of formula (I) + mesotrione, compound of formula (I) + metam, compound of formula (I) + metamifop, compound of formula (I) + metamitron, compound of formula (I) + metazachlor, compound of formula (I) + metazosulfuron, compound of formula (I) + methabenzthiazuron, compound of formula (I) + methazole, compound of formula (I) + methiozolin, compound of formula (I) + methylarsonic acid, compound of formula (I) + methyldymron, compound of formula (I) + methyl isothiocyanate, compound of formula (I) + metobenzuron, compound of formula (I) + metobromuron, compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + metosulam, compound of formula (I) + metoxuron, compound of formula (I) + metribuzin, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + MK-616, compound of formula (I) + molinate, compound of formula (I) + monolinuron, compound of formula (I) + monosulfuron, compound of formula (I) + monosulfuron-ester, compound of formula (I) + MSMA, compound of formula (I) + naproanilide, compound of formula (I) + napropamide, compound of formula (I) + naptalam, compound of formula (I) + NDA-402989, compound of formula (I) + neburon, compound of formula (I) + nicosulfuron, compound of formula (I) + nipyraclofen, compound of formula (I) + n- methyl glyphosate, compound of formula (I) + nonanoic acid, compound of formula (I) + norflurazon, compound of formula (I) + oleic acid (fatty acids), compound of formula (I) + orbencarb, compound of formula (I) + orthosulfamuron, compound of formula (I) + oryzalin, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + oxasulfuron, compound of formula (I) + oxaziclomefone, compound of formula (I) + oxyfluorfen, compound of formula (I) + paraquat, compound of formula (I) + paraquat dichloride, compound of formula (I) + pebulate, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pentachlorophenol, compound of formula (I) + pentanochlor, compound of formula (I) + pentoxazone, compound of formula (I) + pethoxamid, compound of formula (I) + petrolium oils, compound of formula (I) + phenmedipham, compound of formula (I) + phenmedipham-ethyl, compound of formula (I) + picloram, compound of formula (I) + picolinafen, compound of formula (I) + pinoxaden, compound of formula (I) + piperophos, compound of formula (I) + potassium arsenite, compound of formula (I) + potassium azide, compound of formula (I) + pretilachlor, compound of formula (I) + primisulfuron, compound of - - formula (I) + primisulfuron-methyl, compound of formula (I) + prodiamine, compound of formula (I) + profluazol, compound of formula (I) + profoxydim, compound of formula (I) + prohexadione- calcium, compound of formula (I) + prometon, compound of formula (I) + prometryn, compound of formula (I) + propachlor, compound of formula (I) + propanil, compound of formula (I) + propaquizafop, compound of formula (I) + propazine, compound of formula (I) + propham, compound of formula (I) + propisochlor, compound of formula (I) + propoxycarbazone, compound of formula (I) + propoxycarbazone-sodium, compound of formula (I) + propyzamide, compound of formula (I) + prosulfocarb, compound of formula (I) + prosulfuron, compound of formula (I) + pyraclonil, compound of formula (I) + pyraflufen, compound of formula (I) + pyraflufen-ethyl, compound of formula (I) + pyrasulfotole, compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyributicarb, compound of formula (I) + pyridafol, compound of formula (I) + pyridate, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + pyrithiobac, compound of formula (I) + pyrithiobac-sodium, compound of formula (I) +

pyroxasulfone, compound of formula (I) + pyroxulam, compound of formula (I) + quinclorac, compound of formula (I) + quinmerac, compound of formula (I) + quinoclamine, compound of formula (I) + quizalofop, compound of formula (I) + quizalofop-P, compound of formula (I) + quizalofop-ethyl, compound of formula (I) + quizalofop-P-ethyl, compound of formula (I) + rimsulfuron, compound of formula (I) + saflufenacil, compound of formula (I) + sethoxydim, compound of formula (I) + siduron, compound of formula (I) + simazine, compound of formula (I) + simetryn, compound of formula (I) + SMA, compound of formula (I) + sodium arsenite, compound of formula (I) + sodium azide, compound of formula (I) + sodium chlorate, compound of formula (I) + sulcotrione, compound of formula (I) + sulfentrazone, compound of formula (I) + sulfometuron, compound of formula (I) + sulfometuron-methyl, compound of formula (I) + sulfosate, compound of formula (I) + sulfosulfuron, compound of formula (I) + sulfuric acid, compound of formula (I) + tar oils, compound of formula (I) + 2,3,6-TBA, compound of formula (I) + TCA, compound of formula (I) + TCA-sodium, compound of formula (I) + tebutam, compound of formula (I) + tebuthiuron, compound of formula (I) + tefuryltrione, compound of formula (I) + tembotrione, compound of formula (I) + tepraloxydim, compound of formula (I) + terbacil, compound of formula (I) + terbumeton, compound of formula (I) + terbuthylazine, compound of formula (I) + terbutryn, compound of formula (I) + thenylchlor, compound of formula (I) + thiazafluron, compound of formula (I) + thiazopyr, compound of formula (I) + thifensulfuron, compound of formula (I) + thiencarbazone, compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + thiobencarb, compound of formula (I) + tiocarbazil, compound of formula (I) + topramezone, compound of formula (I) + tralkoxydim, compound of formula (I) + triafamone, compound of formula (I) + tri-allate, compound of formula (I) + triasulfuron, compound of formula (I) + triaziflam, compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + tricamba, compound of formula (I) + triclopyr, compound of formula (I) + trietazine, compound of formula (I) + trifloxysulfuron, compound of - - formula (I) + trifloxysulfuron-sodium, compound of formula (I) + trifluralin, compound of formula (I) + triflusulfuron, compound of formula (I) + triflusulfuron-methyl, compound of formula (I) + trifop, compound of formula (I) + trifop-methyl, compound of formula (I) + trihydroxytriazine, compound of formula (I) + trinexapac-ethyl, compound of formula (I) + tritosulfuron, compound of formula (I) + [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3- yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31-6), compound of formula (I) + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl-1 ,3- cyclohexanedione and the compound of formula (I) + VX-573.

In particular, the following mixtures are important: mixtures of a compound of formula (I) with an acetanilide (e.g. compound of formula (I) + acetochlor, compound of formula (I) + dimethenamid, compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, or compound of formula (I) + pretilachlor) or with other inhibitors of very long chain fatty acid esterases (VLCFAE) (e.g. compound of formula (I) + pyroxasulfone); mixtures of a compound of formula (I) with an HPPD inhibitor (e.g. compound of formula (I)

+ isoxaflutole, compound of formula (I) + mesotrione, compound of formula (I) + pyrasulfotole, compound of formula (I) + sulcotrione, compound of formula (I) + tembotrione, compound of formula (I) + topramezone, compound of formula (I) + bicyclopyrone); mixtures of a compound of formula (I) with a triazine (e.g. compound of formula (I) + atrazine, or compound of formula (I) + terbuthylazine); mixtures of a compound of formula (I) with glyphosate; mixtures of a compound of formula (I) with glufosinate-ammonium; mixtures of a compound of formula (I) with a PPO inhibitor (e.g. compound of formula (I) + acifluorfen-sodium, compound of formula (I) + butafenacil, compound of formula (I) +

carfentrazone-ethyl, compound of formula (I) + cinidon-ethyl, compound of formula (I) + flumioxazin, compound of formula (I) + fomesafen, compound of formula (I) + lactofen, or compound of formula (I) + SYN 523 ([3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo- 1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester) (CAS RN 353292- 31-6)). Whilst two-way mixtures of a compound of formula (I) and another herbicide are explicitly disclosed above, the skilled man will appreciate that the invention extends to three-way, and further multiple combinations comprising the above two-way mixtures. In particular, the invention extends to: mixtures of a compound of formula (I) with a triazine and an HPPD inhibitor (e.g.

compound of formula (I) + triazine + isoxaflutole, compound of formula (I) + triazine + mesotrione, - - compound of formula (I) + triazine + pyrasulfotole, compound of formula (I) + triazine + sulcotrione, compound of formula (I) + triazine + tembotrione, compound of formula (I) + triazine + topramezone, compound of formula (I) + triazine + bicyclopyrone; mixtures of a compound of formula (I) with glyphosate and an HPPD inhibitor (e.g.

compound of formula (I) + glyphosate + isoxaflutole, compound of formula (I) + glyphosate + mesotrione, compound of formula (I) + glyphosate + pyrasulfotole, compound of formula (I) + glyphosate + sulcotrione, compound of formula (I) + glyphosate + tembotrione, compound of formula (I) + glyphosate + topramezone, compound of formula (I) + glyphosate + bicyclopyrone; mixtures of a compound of formula (I) with glufosinate-ammonium and an HPPD inhibitor (e.g. compound of formula (I) + glufosinate-ammonium + isoxaflutole, compound of formula (I) + glufosinate-ammonium + mesotrione, compound of formula (I) + glufosinate-ammonium + pyrasulfotole, compound of formula (I) + glufosinate-ammonium + sulcotrione, compound of formula (I) + glufosinate-ammonium + tembotrione, compound of formula (I) + glufosinate- ammonium + topramezone, compound of formula (I) + glufosinate-ammonium + bicyclopyrone; mixtures of a compound of formula (I) with a VLCFAE inhibitor and an HPPD inhibitor (e.g. compound of formula (I) + S-metolachlor + isoxaflutole, compound of formula (I) + S-metolachlor + mesotrione, compound of formula (I) + S-metolachlor + pyrasulfotole, compound of formula (I) + S-metolachlor + sulcotrione, compound of formula (I) + S-metolachlor + tembotrione, compound of formula (I) + S-metolachlor + topramezone, compound of formula (I) + S- metolachlor + bicyclopyrone, compound of formula (I) + acetochlor + isoxaflutole, compound of formula (I) + acetochlor + mesotrione, compound of formula (I) + acetochlor + pyrasulfotole, compound of formula (I) + acetochlor + sulcotrione, compound of formula (I) + acetochlor + tembotrione, compound of formula (I) + acetochlor + topramezone, compound of formula (I) + acetochlor + bicyclopyrone, compound of formula (I) + pyroxasulfone + isoxaflutole, compound of formula (I) + pyroxasulfone + mesotrione, compound of formula (I) + pyroxasulfone +

pyrasulfotole, compound of formula (I) + pyroxasulfone + sulcotrione, compound of formula (I) + pyroxasulfone + tembotrione, compound of formula (I) + pyroxasulfone + topramezone, compound of formula (I) + pyroxasulfone + bicyclopyrone, compound of formula (I) + S- metholachlor + mesotrione + bicyclopyrone; mixtures of a compound of formula (I) with glyphosate and a VLCFAE inhibitor (e.g.

compound of formula (I) + glyphosate + S-metolachlor, compound of formula (I) + glyphosate + acetochlor, compound of formula (I) + glyphosate + pyroxasulfone).

Particularly preferred are mixtures of the compound of formula (I) with mesotrione, bicyclopyrone, isoxaflutole, tembotrione, topramezone, sulcotrione, pyrasulfotole, metolachlor, S- metolachlor, acetochlor, pyroxasulfone, P-dimethenamid, dimethenamid, flufenacet, pethoxamid, atrazine, terbuthylazine, bromoxynil, metribuzin, amicarbazone, bentazone, ametryn, hexazinone, diuron, tebuthiuron, glyphosate, paraquat, diquat, glufosinate, acifluorfen-sodium, butafenacil, carfentrazone-ethyl, cinidon-ethyl, flumioxazin, fomesafen, lactofen, [3-[2-chloro-4-fluoro-5-(1- - - methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,44etrahydropyrimidin-3-yl)phenoxy

acid ethyl ester.

The mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. The reference to acifluorfen-sodium also applies to acifluorfen, the reference to dimethenamid also applies to dimethenamid-P, the reference to glufosinate-ammonium also applies to glufosinate, the reference to bensulfuron-methyl also applies to bensulfuron, the reference to cloransulam-methyl also applies to cloransulam, the reference to flamprop-M also applies to flamprop, and the reference to pyrithiobac-sodium also applies to pyrithiobac, etc. The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 :

100 to 1000: 1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) with the mixing partner). The compounds of formula (I) according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of a compound of formula (I) according to the invention with one or more further active ingredients, in particular with one or more further herbicides, can also be used in combination with one or more safeners. The term "safener" as used herein means a chemical that when used in combination with a herbicide reduces the undesirable effects of the herbicide on non-target organisms, for example, a safener protects crops from injury by herbicides but does not prevent the herbicide from killing the weeds. Where a compound of formula (I) is combined with a safener, the following combinations of the compound of formula (I) and the safener are particularly preferred. Compound of formula (I) + AD 67 (MON 4660), compound of formula (I) + benoxacor, compound of formula (I) + cloquintocet- mexyl, compound of formula (I) + cyometrinil and a compound of formula (I) + the corresponding (Z) isomer of cyometrinil, compound of formula (I) + cyprosulfamide (CAS RN 221667-31-8), compound of formula (I) + dichlormid, compound of formula (I) and dicyclonon, compound of formula (I) and dietholate, compound of formula (I) + fenchlorazole-ethyl, compound of formula (I) + fenclorim, compound of formula (I) + flurazole, compound of formula (I) + fluxofenim, compound of formula (I) + furilazole and a compound of formula (I) + the corresponding R isomer or furilazome, compound of formula (I) + isoxad if en-ethyl, compound of formula (I) + mefenpyr- diethyl, compound of formula (I) and mephenate, compound of formula (I) + oxabetrinil, compound of formula (I) + naphthalic anhydride (CAS RN 81-84-5), compound of formula (I) and TI-35, compound of formula (I) + N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4) and a compound of formula (I) + N-(2-methoxybenzoyl)-4-

[(methylaminocarbonyl)amino]benzenesulfonamide. Particularly preferred are mixtures of a compound of formula (I) with benoxacor, a compound of formula (I) with cloquintocet-mexyl, a - - compound of formula (I) + cyprosulfamide and a compound of formula (I) with N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.

The safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. The reference to cloquintocet-mexyl also applies to cloquintocet and to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO02/34048 and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.

Preferably the mixing ratio of compound of formula (I) to safener is from 100: 1 to 1 :10, especially from 20: 1 to 1 : 1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) and any further active ingredient, in particular a further herbicide, with the safener).

It is possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied simultaneously. For example, the safener, a compound of formula (I) and one or more additional herbicide(s), if any, might be applied to the locus pre-emergence or might be applied to the crop post-emergence. It is also possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied sequentially. For example, the safener might be applied before sowing the seeds as a seed treatment and a compound of formula (I) and one or more additional herbicides, if any, might be applied to the locus pre-emergence or might be applied to the crop post-emergence.

Preferred mixtures of a compound of formula (I) with further herbicides and safeners include:

Mixtures of a compound of formula (I) with S-metolachlor and a safener, particularly benoxacor.

Mixtures of a compound of formula (I) with isoxaflutole and a safener.

Mixtures of a compound of formula (I) with mesotrione and a safener.

Mixtures of a compound of formula (I) with sulcotrione and a safener.

Mixtures of a compound of formula (I) with tembotrione and a safener. Mixtures of a compound of formula (I) with topramezone and a safener.

Mixtures of a compound of formula (I) with bicyclopyrone and a safener.

Mixtures of a compound of formula (I) with a triazine and a safener. Mixtures of a compound of formula with a triazine and isoxaflutole and a safener.

Mixtures of a compound of formula with a triazine and mesotrione and a safener.

Mixtures of a compound of formula with a triazine and sulcotrione and a safener.

Mixtures of a compound of formula with a triazine and tembotrione and a safener.

Mixtures of a compound of formula with a triazine and topramezone and a safener.

Mixtures of a compound of formula with a triazine and bicyclopyrone and a safener.

Mixtures of a compound of formula with glyphosate and a safener.

Mixtures of a compound of formula with glyphosate and isoxaflutole and a safener.

Mixtures of a compound of formula with glyphosate and mesotrione and a safener.

Mixtures of a compound of formula with glyphosate and sulcotrione and a safener.

Mixtures of a compound of formula with glyphosate and tembotrione and a safener.

Mixtures of a compound of formula with glyphosate and topramezone and a safener.

Mixtures of a compound of formula with glyphosate and bicyclopyrone and a safener.

Mixtures of a compound of formula with glufosinate-ammonium and a safener.

Mixtures of a compound of formula with glufosinate-ammonium and isoxaflutole and a safener.

Mixtures of a compound of formula with glufosinate-ammonium and mesotrione and a safener.

Mixtures of a compound of formula with glufosinate-ammonium and sulcotrione and a safener.

Mixtures of a compound of formula with glufosinate-ammonium and tembotrione and a safener.

Mixtures of a compound of formula with glufosinate-ammonium and topramezone and safener.

Mixtures of a compound of formula with glufosinate-ammonium and bicyclopyrone and safener.

Mixtures of a compound of formula with S-metolachlor and a safener. Mixtures of a compound of formula with S-metolachlor and isoxaflutole and a safener. Mixtures o a compound of formula with S-metolachlor and mesotrione and a safener. Mixtures o a compound of formula with S-metolachlor and sulcotrione and a safener. Mixtures o a compound of formula with S-metolachlor and tembotrione and a safener. Mixtures o a compound of formula with S-metolachlor and topramezone and a safener. Mixtures o a compound of formula with S-metolachlor and bicyclopyrone and a safener. Mixtures o a compound of formula with pyroxasulfone and a safener. Mixtures o a compound of formula with pyroxasulfone and isoxaflutole and a safener. Mixtures o a compound of formula with pyroxasulfone and mesotrione and a safener. Mixtures o a compound of formula with pyroxasulfone and sulcotrione and a safener. Mixtures o a compound of formula with pyroxasulfone and tembotrione and a safener. Mixtures o a compound of formula with pyroxasulfone and topramezone and a safener. Mixtures o a compound of formula with pyroxasulfone and bicyclopyrone and a safener. Mixtures o a compound of formula with acetochlor and a safener. Mixtures o a compound of formula with acetochlor and isoxaflutole and a safener. Mixtures o a compound of formula with acetochlor and mesotrione and a safener. Mixtures o a compound of formula with acetochlor and sulcotrione and a safener. Mixtures o a compound of formula with acetochlor and tembotrione and a safener. Mixtures o a compound of formula with acetochlor and topramezone and a safener. Mixtures o a compound of formula with acetochlor and bicyclopyrone and a safener. Mixtures o a compound of formula with S-metolachlor and mesotrione and

bicyclopyrone and a safener

Mixtures o a compound of formula with S-metolachlor and a triazine and mesotrione and bicyclopyrone and a safener.

Where the compound of formula (I) is referred to above in relation to other herbicidal mixing partners and/or safeners, this may be replaced with the compound of formula (la) such that all the herbicidal and safener mixes listed above also apply, individually, to the compound of formula (la). - -

Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention.

For the avoidance of doubt, where a literary reference, patent application, or patent, is cited within the text of this application, the entire text of said citation is herein incorporated by reference.

Examples

Preparation Examples The following abbreviations were used in this section: s = singlet; bs = broad singlet; d = doublet; dd = double doublet; dt = double triplet; t = triplet, tt = triple triplet, q = quartet, sept = septet; m = multiplet; RT = retention time, MH⁺ = molecular mass of the molecular cation.

1 H NMR spectra were recorded at 400 MHz either on a Varian Unity Inova instrument or Bruker AVANCE - II instrument. The compounds may exist in a mixture of diastereoisomers, which may be observed by

LC-MS and NMR. The stereochemistry of the chiral centre at the carbon containing the R₃ group was generally found to interconvert in solution at room temperature. Depending on the nature of R₂ substitution and the conditions for product synthesis, purification and analysis the ratio of diastereromers may change. Table 1 lists examples of compounds of the general formula (I)

(I) wherein R^b, R^c, R², R³ and X are as defined above.

These compounds were made by the general methods described.

Example 1 : (4R)-1 -(5-ferf-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2- one (A2) - -

Procedure for s nthesis of phenyl N-(5-ferf-butylisoxazol-3-yl)carbamate (Step 1)

To a mixture of 5-ieri-butylisoxazol-3-amine (commercially available) (89.54g, 638.70 mmol) in DCM (900 mL) was added N,N'-diisopropylethylamine (1.1 equiv., 702.57 mmol) and the mixture was stirred until homogeneous. Phenyl chloroformate (100 g, 638.7001 mmol) was charged to a dropping funnel and added to the reaction dropwise over 1 hour with care taken so the temperature never rose above 30°C. The reaction was stirred a further 2h. This mixture was then used as is in the next step.

LC-MS: (positive ES MH+ 261 ).

Procedure for synthesis of 1 - 5-ferf-butylisoxazol-3-yl)-3-methyl-urea (Step 2)

Phenyl N-(5-ieri-butylisoxazol-3-yl)carbamate (crude solution in DCM from previous step) was carefully added to a methylamine (2M in methanol) solution keeping the temperature below 25°C. After 1 h, the solution was washed with water (2 x 1 L), aqueous sodium hydroxide (5%, 2 x 1 L) and finally with brine. The solution was evaporated to give a brown oil which then crystallised and could be recrystallized (EtOAc (770 mL) + isohexane (400 mL)) to give product (63g, 50% over 2 steps) as a white solid.

LC-MS: (positive ES MH+ 198). - -

Procedure for synthesis of 1-(5-ferf-butylisoxazol-3-yl)-4,5-dihydroxy-3-methyl- imidazolidin-2-one (Step 3

1-(5-ieri-butylisoxazol-3-yl)-3-methyl-urea (100 g, 507.00 mmol) and glyoxal (40% aqueous solution, 1.2 equiv. 69.78 mL) were combined with water (1 L). The mixture was refluxed until all solid had dissolved (1 h 40mins) and was then left to cool overnight. During this time the product had crystallised. The mixture was extracted with ethyl acetate (1 x 1 L and then 2 x 500ml). The EtOAc extracts were dried (MgS0₄) and evaporated, giving product as an off-white powder (122.7 g), which was used with further purification.

LC-MS: (positive ES MH+ 256).

Procedure for synthesis of (4 ?)-1-(5-ferf-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl- imidazolidin-2-one and (4S)-1 -(5-ferf-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl- imidazolidin-2-one Step 4)

1-(5-ieri-butylisoxazol-3-yl)-4,5-dihydroxy-3-methyl-imidazolidin-2-one (2 g, 7.83 mmol) and 4- methylbenzenesulfonic acid (20 mg, 0.12 mmol) were refluxed in ethanol (20 mL) for 40 mins. The reaction mixture was then evaporated, redissolved in DCM and purified by flash chromatography eluting with ethyl acetate in hexane. Fractions containing product were evaporated to give racemic product 1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl- imidazolidin-2-one (1.48g) as a colourless oil, which crystallised on standing overnight. 1 -(5-tert- butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one) was separated into individual enantiomers E1 and E2 by preparative chiral HPLC (CHIRALPAK IC column, eluting with isoHexane (containing IPA) and IPA MeOH). The second eluting enantiomer was proved by X- ray crystallography to be (4S,5S)-1-(5-ieri-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl- imidazolidin-2-one and so the first eluting enantiomer must be the desired product ((4R,5R)-1-(5- ieri-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one).

Data for (4R,5R)-1-(5-ieri-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one: - -

Ή NMR (400 MHz, CDCI₃) δ 6.60 (s, 1 H), 5.55 (d, 1 H), 4.70 (s, 1 H), 4.14 (d, 1 H), 3.62 (ddd, 2H), 2.96 (s, 3H), 1.34 (s, 9H), 1.26 (t, 3H).

LC-MS: (positive ES MH+ 284).

Example 2: (4 ?)-1 -(5-ferf-butylisoxazol-3-yl)-5-hydroxy-4-(methoxymethyl)-3-methyl- imidazolidin-2-one (A4)

Procedure for synthesis of 1 1,3-trimethoxy-N-methyl-propan-2-amine (Step 1)

A solution of 2-bromo-1 , 1 ,3-trimethoxy-propane (commercially available) (7 g, 32.85 mmol) in methylamine (40 % aqueous solution) (105 mL, 210 mmol) was divided into seven equal portions and these were heated at 130°C for 1 h in a microwave. The combined reaction mixtures were then concentrated and the residue obtained was treated with toluene and evaporated again. The residue was then stirred with DCM, filtered and evaporated to give the crude product that was taken to next step without further purification.

Procedure for synthesis of 3-(5-tert-butylisoxazol-3-yl)-1-[2,2-dimethoxy-1- (methoxymethyl)ethyl]-1 -methyl-urea (Step 2)

A mixture of crude 1 , 1 ,3-trimethoxy-N-methyl-propan-2-amine (5 g, 12.25 mmol) in dichloromethane (50 mL) was treated with triethylamine (3.38 mL, 24.51 mmol) and phenyl N-(5- - - ieri-butylisoxazol-3-yl)carbamate (3.19 g, 12.253 mmol) and stirred at rt for 18 h. The reaction mixture was evaporated to give crude product (2.8 g), which was used without further purification. LC-MS: (positive ES MH+ 330). Procedure for synthesis of 1- 5-ferf-butylisoxazol-3-yl)-3-methyl-urea (Step 3)

A mixture of 3-(5-ieri-butylisoxazol-3-yl)-1-[2,2-dimethoxy-1-(methoxymethyl)ethyl]-1 -methyl-urea (2.8 g, 6.8 mmol) in acetic acid (28 mL) was treated with water (14 mL) and then heated at 80°C h for 2 h. The reaction mixture was then evaporated, treated with toluene, re-evaporated and these last two steps were repeated. The residue obtained was then purified by flash chromatography to give racemic product 1-(5-tert-butylisoxazol-3-yl)-5-hydroxy-4- (methoxymethyl)-3-methyl-imidazolidin-2-one (1.2g, 62%).

LC-MS: (positive ES MH+ 284). Procedure for synthesis of (4 ?)-1-(5-ferf-butylisoxazol-3-yl)-5-hydroxy-4-(methoxymethyl)- 3-methyl-imidazolidin-2-one (A4) (Step 4)

1-(5-ieri-butylisoxazol-3-yl)-5-hydroxy-4-(methoxymethyl)-3-methyl-imidazolidin-2-one was separated into individual enantiomers E1 and E2 by preparative chiral HPLC (CHIRALPAK IC column, eluting with isoHexane (containing IPA) and IPA MeOH). The first eluting enantiomer was assigned as (4R)-1-(5-tert-butylisoxazol-3-yl)-5-hydroxy-4-(methoxymethyl)-3-methyl- imidazolidin-2-one by analogy with other compounds.

1 H NMR (400MHz, CDCI₃) δ 6.64 (s, 1 H), 5.62 (t, 1 H), 4.14 (d, 1 H), 3.58-3.53 (m, 3H), 3.38 (s, 3H), 2.94 (s, 3H), 1.33 (s, 9H).

LC-MS: (positive ES MH+ 284). - -

Table 1

- -

Example 3a: Pre-emerqence herbicidal activity

Seeds of a variety of test species were sown in standard soil in pots. After cultivation for one day (pre-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). The test plants were then grown in a glasshouse under controlled conditions (at 24/16°C, day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days, the test was evaluated (5= total damage to plant; 0 = no damage to plant). Results are shown in Table 2. Table 2: Application pre-emerqence

( Example I Rate AMARE j ZEAMX j ECHCG j LOLPE SETFA j ABUTH - -

Example 3b: Post-emergence herbicidal activity

Seeds of a variety of test species were sown in standard soil in pots. After 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). The test plants were then grown in a glasshouse under controlled conditions (at 24/16°C, day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days, the test was evaluated (5 = total damage to plant; 0 = no damage to plant). Results are shown in Table 3.

Table 3: Application post-emergence

ABUTH = Abutilon theophrasti; AMARE = Amaranthus retroflexus; SETFA = Setaria faberi; ALOMY = Alopecurus myosuroides; ECHCG = Echinochloa crus-galli; ZEAMX = Zea mays.

Example 4: Comparison of enantiomers

Pre- and post-emergence testing was carried out as detailed above on the compounds A1 , A2, A4 and A5 and their respective S-enantiomers. Results are shown in Tables 4 and 5.

Table 4: Comparison of enantiomers, pre-emergence

- -

Table 5: Comparison of enantiomers, post-emergence

-enan omer

ABUTH = Abutilon theophrasti; AMARE = Amaranthus retroflexus; SETFA = Setaria faberi; ALOMY = Alopecurus myosuroides; ECHCG = Echinochloa crus-galli; ZEAMX = Zea mays.

Claims

1. A compound of the formula (I)

(I)

wherein

X is selected from S and O;

R^b is selected from Ci-C₆ alkyl, Ci-C₆ cyanoalkyl, C₃-C₆ cycloalkyl, C₃-C₆ cyanocycloalkyl, d-C₆ haloalkyl, d-C₆ alkylthio,

R^c is selected from hydrogen, halogen, cyano, Ci-C₆ alkyl or Ci-C₆ haloalkyl; or R^b and R^c together with the carbon atoms to which they are attached form a 3-7 membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms independently selected from S, O and N and optionally substituted with from 1 to 3 groups independently selected from halogen, Ci-C₆ alkyl and Ci-C₆ haloalkyl;

R² is selected from Ci-C₄ alkoxy, Ci-C₄ alkoxy-Ci-C₄ alkyl;

R³ is selected from halogen, hydroxyl, -NR⁵R⁶, or any one of the following groups

R⁵ and R⁶ are independently selected from hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, C₂-C₂o alkenyl, C₂-C₂₀ alkynyl, or R⁵ and R⁶ together with the carbon atoms to which they are attached form a 3-6 membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms independently selected from S, O and N and optionally substituted with from 1 to 3 groups independently selected from halogen and Ci-C₆ alkyl;

R⁷ and R⁸ are independently selected from hydrogen, Ci-C₆ alkyl, Ci-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, a C₅-Ci₀ heteroaryl group which can be mono- or bicyclic comprising from 1 to 4 heteroatoms independently selected from N, O and S and optionally substituted with 1 to 3 groups independently selected from halogen, C₁-C3 alkyl, C₁-C3 haloalkyl and C₁-C3 alkoxy, a C₆-Ci₀ aryl group optionally substituted with 1 to 3 groups independently selected from halogen, nitro, cyano, C₁-C3 alkyl, Ci-C₃ alkoxy, Ci-C₃ haloalkyl and Ci-C₃ haloalkoxy, or R⁷ and R⁸ together with the atoms to which they are attached form a 3-6 membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms independently selected from S, O and N and optionally substituted with from 1 to 3 groups independently selected from halogen or Ci-C₆ alkyl;

R⁹ is selected from Ci-C₆ alkyl or benzyl optionally substituted with 1 to 3 groups independently selected from halogen, nitro, cyano, Ci-C₃ alkyl, Ci-C₃ alkoxy, Ci-C₃ haloalkyl and Ci-C₃ haloalkoxy; or an N-oxide or salt form thereof and wherein the dihydro-hydantoin ring carbon to which R² is attached has the R-stereochemistry as depicted.

2. The compound of claim 1 , wherein X is O.

3. The compound of claim 1 or claim 2, wherein R^b is selected from Ci-C₆ alkyl, Ci-C₆ cyanoalkyl, C₃-C₆ cycloalkyl, C₃-C₆ cyanocycloalkyl, Ci-C₆ haloalkyl and Ci-C₆ alkylthio.

4. The compound of claim 3, wherein R^b is selected from Ci-C₄ alkyl, Ci-C₄ cyanoalkyl, C₃-C₆ cycloalkyl, C₃-C₆ cyanocycloalkyl, Ci-C₄ haloalkyl and C₁-C4 alkylthio.

5. The compound of claim 4, wherein R^b is selected from Ci-C₄ alkyl or Ci-C₄ haloalkyl.

6. The compound of claim 5, wherein R^b is tert-butyl or 1-fluoro-1 -methyl-ethyl.

7. The compound of any one of claims 1 to 6, wherein R^c is selected from hydrogen, chloro, fluoro, bromo, cyano, Ci-C₄ alkyl and Ci-C₄ haloalkyl.

8. The compound of claim 7, wherein R^c is hydrogen, chloro, fluoro, cyano or methyl.

9. The compound of claim 8, wherein R^c is hydrogen.

10. The compound of any one of claims 1 to 9, wherein R² is selected from C1-C3 alkoxy and C1-C3 alkoxy-Ci-C₃ alkyl.

1 1. The compound of claim 10, wherein R² is selected from methoxy, ethoxy, propyloxy, methoxymethyl, ethoxymethyl and methoxyethyl.

12. The compound of claim 1 1 , wherein R² is selected from methoxy, ethoxy and propyloxy.

13. The compound of any one of claims 1 to 12, wherein R³ is selected from hydroxyl, -NR⁵R⁶, halogen, Ci-C₆ alkylcarbonyloxy, Ci-C₆ alkoxycarbonyloxy or aryloxycarbonyloxy wherein the aryl group may be substituted with 1 to 3 groups independently selected from halogen, nitro, cyano, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl and C1-C3 haloalkoxy

14. The compound of claim 13, wherein R³ is selected from hydroxyl, -NR⁵R⁶ or halogen.

15. The compound of claim 14, wherein R³ is hydroxyl.

16. A compound of formula (la):

(la)

wherein

X, R^b, R^c, and R³ are as defined in claims 1 to 9 and 13 to 15 and R² is selected from ethoxy, propyloxy and C1-C4 alkoxy-Ci-C₄ alkyl or an N-oxide or salt form thereof.

17. The compound of claim 16, wherein R² is selected from methoxy, ethoxy, propyloxy, methoxymethyl, ethoxymethyl and methoxyethyl.

18. The compound of claim 17, wherein R² is selected from methoxy, ethoxy and propyloxy.

19. A herbicidal composition comprising a compound of formula (I) or (la) as defined in any one of claims 1 to 18 together with at least one agriculturally acceptable adjuvant or diluent.

20. A composition according to claim 19 which comprises a further herbicide in addition to the compound of formula (I) or (la).

21. A composition according to claim 19 or 20 which comprises a safener.

22. Use of a compound of formula (I) or (la) as defined in any one of claims 1 to 18 or a composition as defined in any one of claims 19 to 21 as a herbicide.

23. A method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a compound of formula (I) or (la) as defined in any one of claims 1 to 18 or a composition as claimed in any one of claims 19 to 21.